Optimizing the Energetics of FLP-Type H<sub>2</sub> Activation by Modulating the Electronic and Structural Properties of the Lewis Acids: A DFT Study
Mojgan Heshmat, Bernd Ensing
Abstract
splitting reaction can be changed from endergonic to exergonic by tuning the electrophilicity of the LA. Also, a more nucleophilic LB results in a more stable ion pair product and a lower barrier for the hydrogen splitting. The bulkiness of the LB leads to an early transition state to reduce steric hindrance and lower the barrier height. The bulkiness of the fragments determines the cavity size in the FLP complex, and a large cavity allows for a larger charge separation in the ion pair configuration. A shorter proton-hydride distance in this product complex correlates with a stronger attraction between the fragments, which forms more reactive ion pairs and facilitates the proton and hydride donations in the subsequent hydrogenation process. These insights may help with rationalizing the experimentally observed reactivities of FLPs and with designing better FLP systems for hydrogenation catalysis and hydrogen storage.